National Institutes of Health: Gender Differences in Radiology Funding.

RATIONALE AND OBJECTIVE: Radiology has traditionally remained one of the most male-dominated specialties, although a higher proportion of women are now beginning to occupy roles as academic radiologists than their male counterparts. The present study investigated trends in National Institutes of Health (NIH) funding within Diagnostic Radiology stratified by gender, and correlated with measures of academic output, including h-index. MATERIALS AND METHODS: Data on funding was obtained from the online NIH Research Portfolio Online Reporting Tools Expenditure and Results for fiscal years 2016-2019, and information regarding each Principal Investigator (PI) was obtained from the Scopus database and departmental websites. Mann-Whitney U tests were performed on collected data for statistical comparison of continuous variables. RESULTS: Of the 2929 grants included in this analysis, 1789 (61.07%) were awarded to male PIs and 1140 (38.9%) to female PIs.  Among PIs holding a PhD degree, male PIs had a higher mean grant amount ($619,807.00) compared to female PIs ($158,486.00). CONCLUSION: Although female representation within academic radiology has been increasing, the mean NIH grants awarded to women is less than that awarded to men. Reasons for this are numerous and may include differential prioritization of career objectives among men and women, although such rationalization is inevitably speculative in nature. Significant gender differences in NIH funding were seen at the PhD level, and the strongest correlation between NIH funding and academic output was observed for the h-index of female PIs. These results underscore the fact that women are ostensibly being held to a higher academic standard than men in terms of funding decisions.

Noncovalent endo-binding of fullerenes to diprotonated bisporphyrins.

Noncovalent binding of fullerenes to bisporphyrins was studied in the gas phase by energy-dependent collision-induced dissociation (CID) with Xe under single-collision conditions. The electrospray ionization mass spectra of calix[4]arene-linked bisporphyrins show that bisporphyrins take up to 3-4 protons, depending on the type of meso-substituents. Of the protonated bisporphyrins, the diprotonated species form stable 1:1 complexes with fullerenes (C(60) and C(70)). CID cracking patterns of the diprotonated bisporphyrins indicate that each monomeric porphyrin moiety is singly protonated. CID yield-energy curves obtained from the 1:1 diprotonated bisporphyrin-fullerene complexes suggest that a fullerene occupies the endo-binding site intercalated between the two singly protonated porphyrin moieties. In the cases of 1:2 diprotonated bisporphyrin-fullerene complexes, CID results show that one fullerene binds inside (endo-binding) and the other outside (exo-binding). The exo-binding mode is energetically almost identical to the binding of fullerenes to singly protonated porphyrin monomers. The endo-binding energy is at least twice the exo-binding energy. To gain insights into the binding mode, we optimized structures of diprotonated bisporphyrins and their 1:1 endo-complexes with fullerenes, and calculated the endo-binding energy for C(60), C(70) (end-on), and C(70) (side-on). The endo-binding of fullerenes to diprotonated bisporphyrins nearly doubles the π-π interactions while reducing the electrostatic repulsion between the two singly protonated porphyrin moieties. The side-on binding of C(70) is favored over the end-on binding because the former exerts less steric strain to the lower rim of calixarene.

Noncovalent binding between fullerenes and protonated porphyrins in the gas phase.

Noncovalent interactions between protonated porphyrin and fullerenes (C60 and C70) were studied with five different meso-substituted porphyrins in the gas phase. The protonated porphyrin-fullerene complexes were generated by electrospray ionization of the porphyrin-fullerene mixture in 3:1 dichloromethane/methanol containing formic acid. All singly protonated porphyrins formed the 1:1 complexes, whereas porphyrins doubly protonated on the porphine center yielded no complexes. The complex ion was mass-selected and then characterized by collision-induced dissociation with Xe. Collisional activation exclusively led to a loss of neutral fullerene, indicating noncovalent binding of fullerene to protonated porphyrin. In addition, the dissociation yield was measured as a function of collision energy, and the energy inducing 50% dissociation was determined as a measure of binding energy. Experimental results show that C70 binds to the protonated porphyrins more strongly than C60, and electron-donating substituents at the meso positions increase the fullerene binding energy, whereas electron-withdrawing substituents decrease it. To gain insight into π-π interactions between protonated porphyrin and fullerene, we calculated the proton affinity and HOMO and LUMO energies of porphyrin using Hartree-Fock and configuration interaction singles theory and obtained the binding energy of the protonated porphyrin-fullerene complex using density functional theory. Theory suggests that the protonated porphyrin-fullerene complex is stabilized by π-π interactions where the protonated porphyrin accepts π-electrons from fullerene, and porphyrins carrying bulky substituents prefer the end-on binding of C70 due to the steric hindrance, whereas those carrying less-bulky substituents favor the side-on binding of C70.

Collision-induced dissociation of II-VI semiconductor nanocrystal precursors, Cd2+ and Zn2+ complexes with trioctylphosphine oxide, sulfide, and selenide.

The metal (M = Cd2+ and Zn2+) complexes with trioctylphosphine chalcogenide (TOPE, E = O, S, and Se) are prepared by electrospray ionization, and their relative stabilities and intramolecular reactions are studied by collision-induced dissociation (CID) with Xe under single collision conditions. These metal-TOPE complexes are considered as molecular precursors for the colloidal synthesis of II-VI compound semiconductor nanocrystals employing TOPO as a metal-coordinating solvent and TOPS or TOPSe as a chalcogen precursor. Of the various [M + nTOPE]2+ (n = 2-7) ions generated by ESI, the n = 2-4 complexes are characterized by CID as a function of collision energy. The collision energy at 50% dissociation (E50%) is determined from the cracking curve and the relative stabilities of the complexes are established. Between the two metal ions, the zinc-TOPE complexes are more stable than the cadmium-TOPE complexes when n = 2-3, whereas their stabilities are reversed when n = 4. Of the TOPE, TOPO binds most strongly to the metal ion, while TOPSe does most weakly. Upon CID, loss of TOPE occurs exclusively from the tetra-TOPE complexes, while extensive fragmentation of TOPE takes place from the di-TOPE complexes, showing the signature of the metal chacogenide formation. The nucleation of nanocrystals appears to begin with cracking of [M + 2TOPE]2+ (E = S and Se).